Detergent containing enzyme and coarse perborate particles

ABSTRACT

BIOLOGICAL DETERGENT COMPOSITION CONTANING A STABLE ENZYME AND A PRECOMPOUND, SUCH AS SODIUM PERBORATE, THE PARTICLES OF WHICH HAVE A SIZE SUCH THAT AT LEAST ABOUT 50% OF THE PARTICLES ARE RETAINED ON A SCREEN HAVING SIEVE OPENINGS OF 0.42 MM. AND LESS THAN 5% OF THE PARTICLES PASS THROUGH A SCREEN HAVING SIEVE OPENINGS OF 0.177 MM.

3,789,001 DETERGENT CONTAINING ENZYME AND COARSE PERBORATE PARTICLESDaniele Painelli, Rome, Italy, assignor to Colgate- Palmolive Company,New York, N-Y. No Drawing. Filed Mar. 9, 1972, Ser. No. 233,311

Int. or. one 7/56 us. 01. 252-99 7 Claims ABSTRACT OF THE DISCLOSUREThis invention relates to a biological detergent composition containingan enzyme. More particularly, the invention relates to a biologicalenzyme detergent composition containing an enzyme and a water-solubleinorganic percompound in which the stability of the enzyme issubstantially improved through the use of percompound of particularsize.

The use ofiggylnismandsparticularly proteolytic enzymes as assistants inthe laundering of clothes with detergent compositions has long beenknown in the art. While compositions containing water-soluble inorganicpercompounds such as sodium perborate, have been suggested, the art hastaught that the presence of the perborate has an inhibitory effect onthe enzyme action, at least during the early period after the detergentcomposition is placed in water. Moreover, the inhibitory effect mayremain at least in part even after the passing of considerable time,such as after soaking overnight.

It is an advantage of the instant invention that the enzyme is renderedconsiderably more stable in a detergent composition which also containsa percompound. Additional advantages of this invention will be apparentfrom the consideration of the following disclosure.

In accordance with certain of its aspects, this invention relates to abiological cleaning composition containing a water-soluble synthetic,organic surface-active agent, an enzyme and a water-soluble inorganicpercompound, having a size such that at least about 50% of the particlesthereof are retained on a screen having sieve openings of 0.42 mm. andless than about of the particles pass through a screen having sieveopenings of 0.177 mm.

In the preferred form of the invention the enzyme comprises aproteolytic enzyme which is active upon protein matter and catalyzesdigestion or degradation of such matter when present as in linen orfabric stain in a hydrolysis reaction. Generally, the enzymes areeffective in a pH range of about 4-12, and are effective even atmoderately high use temperatures. They are also effective at ambienttemperature and temperatures above about 10 C. Particular examples ofproteolytic enzymes which vmay be used in the instant invention includepepsin,

trypsin, chymotrypsin, papain, bromelin, colleginase, keratinase,carboxylase, amino peptidase, elastase, subtilisin andaspergillopepidase A and B. Preferred enzymes are subtilisin enzymesmanufactured and cultured from special strains of spore formingbacteria, particularly Bacillus subtilis.

Proteolytic enzymes such as Alcalase, Maxatase, Protease AP, ProteaseATP 40, Protease ATP 120, Protease L-252 and Protease L-423 are amongthose enzymes derived from strains of spore foaming bacillus, such asBacillus subtilis.

United States Patent 0 ice Different proteolytic enzymes have differentdegrees of effectiveness in aiding in the removal of stains fromtextiles and linen. Particularly preferred as stain removing enzymes aresubtilisin enzymes.

Metalloproteases which contain divalent ions such as calcium, magnesiumor zinc bound to their protein chains are also of interest.

The production of various proteolytic enzyme concentrates is describedin the patent literature: For example in Laid Open German specification1,800,508 and in published Netherlands patent application 6815944.

The enzymes described in Laid Open German specification 1,800,508 areproteases of the serine type produced by culture of the genus Bacillusand show optimum proteolytic activity against hemoglobin at a pH higherthan 9 (e.g. pH 10, 10.5, 11 or 12). Particularly suitable is the enzymedesignated in that specification as C372 or the enzyme sold by NovoIndustry A/S as SP-72. It is noteworthy, that this serine type of enzymeis highly effective with inorganic percompounds in accordance with thisinvention.

The enzyme preparations are generally extremely fine powders. In atypical powdered enzyme preparation the particle diameter generallyranges from 0.01 mm. to 0.15 mm., e.g., about 0.1 mm. and as much as ofthe material may pass through a 100 mesh (U.S. Standard) sieve. On theother hand the spray dried granules are usually of very much largerparticle size, with the major portion of the granules being from about0.2 mm. to 2.0 mm. in diameter.

The enzyme preparations are generally diluted with inorganic salts,e.g., alkali metal and alkaline earth metal salts. Typically the enzymecomprises from 1% to by weight of the enzyme preparation. For example, atypical Alcalase enzyme material analyzes (by weight) 6.5% enzyme, 4%water, 70% sodium chloride, 15.5% sodium sulfate, 3.5% calcium sulfate,and 0.5% organic impurities. Chemically they are typically stable in thepH range of 5 to 10, particularly at an alkaline pH of 8.0 to 9.Generally, they are effective against various types of soil in anaqueous medium having a temperature of about 20 C. to about 80 C.Naturally, different proteolytic enzymes have different degrees ofeffectiveness in aiding in the removal of specific stains from textilesand linen.

Instead of, or in addition to, the proteolytic enzyme, an amylase may bepresent such as a bacterial amylase of the alpha type (e.g. obtained byfermentation of B. subtilis). One very suitable enzyme mixture containsboth a bacterial amylase of the alpha type and an alkaline protease,preferably in proportions to supply about 100,- 000 to 400,000 Novoalpha-amylase units per Anson unit of said alkaline protease.

' The amount of enzyme product present in the detergent compositionwill, of course, depend to some extent on the amount of detergentcomposition which is to be added to the wash water. For detergentcompositions which are intended for use in concentrations of about 0.15%in the wash water of an automatic home laundering machine, one suitableamount of granular enzyme product is such as to provide one Anson unitof alkaline centration may correspond to about 0.003-0.012 Anson unitsper liter of wash water, or in a detergent formulation designed for useat a concentration of 1.5 grams per liter of wash water, about 0002-0008Anson units per gram of detergent formulation. Typically the enzymeamounts to about 01-10% by weight of the detergent.

' ing water on a blend of enzyme and hydratable builder salt to hydratethe salt and form granules. The binding of enzyme and detergent buildersalt such as sodium tripolyphosphate may also take place by granulatingan enzyme preparation and the hydratable builder salt in the presence ofice particles at a temperature below about 30 C. to produce a granule inwhich the hydratable builder salt is substantially completely hydratedand the thermal degradation of the enzyme is minimized.

Another alternate process for producing a granular enzyme productcomprises granulating an enzyme in particulate form and a builder saltin particulate form with an aqueous solution of a nonionic organicsurface-active agent using an amount of water at least sufiicient tosubstantially completely hydrate the builder salt.

A further highly desirable process for producing enzyme product ofreduced dustiness comprises spraying a blend of molten nonionicdetergent and enzyme concentrate into cool air to form tiny sphericalbeads.

Further techniques and process for producing granular enzyme products ofreduced dustiness are known to those skilled in the art.

In accordance with this invention, the water-soluble percompound may bean alkali metal perborate such as sodium perborate tetrahydrate, sodiumperborate monohydrate, lithium perborate, potassium perborate, bariumperborate, calcium perborate, as well as water soluble alkali metal andalkaline earth metal percarbonates, perphosphates, and persulfates.

The preferred percompounds are sodium perborates.

A preferred range of proportions of the perborate is one which providesa concentration of percompound in the wash water equivalent to about '1to 60 p.p.m., more preferably about 4 to 50 p.p.m., e.g., 7 to 45p.p.m., of available oxygen; about 45 p.p.m. have thus far given bestresults. In sodium perborate tetrahydrate (NaBO -4H O) the availableoxygen content (or peroxy oxygen content) is about 10% i.e., one atom ofavailable oxygen per molecule'of the perborate. The proportions ofperborate for use in the detergent formulation can therefore readily becalculated if one knows how much of the total formulation is to be addedto the wash water. Commercial detergent formulations are often designedfor use in proportions in the range of about 01-02% in the Wash water(e.g. at 0.15% concentration), a preferred detergent formulationcontaining sodium perborate tetrahydrate designed for use at the 0.15%concentration in the wash water will therefore contain approximately 5to 30% of that compound, corresponding roughly to the 7 to 45 p.p.m. ofavailable oxygen.

In accordance with this invention, the size of the particles ofpercompound employed is such that at least 50% of the particles areretained on a screen having sieve Openings of 0.42 mm. and less thanabout 5% of the particles are small enough to pass through a screenhaving sieve openings of 0.177 mm. The larger particles of perborateshould be such that they are sufiiciently soluble to easily dissolve inwater with the remainder of the detergent, and that they do notsegregate from other components of the detergent mixture. Typically,substantially all the particles which pass through a screen having sieveopenings of 0.84 mm. as larger particles would tend to segregate.

If the percentage of particles of percompound which pass through ascreen having sieve openings of 0.177 mm. is substantially greater than5%, some improvement in enzyme stability may be noted so long as atleast half of the particles would be retained on the screen having sieveopenings of 0.42 mm. Substantially improved enzyme stability is apparentwhen the percentage of small particles pass through a screen havingsieve openings of 0.177 mm. is less than about 5% and particularly whenthere are ubstantially no fines at all which pass through a screenhaving sieve openings of 0.177 mm.

The degree of improvement of enzyme stability may also vary somewhatdepending on the type of enzyme employed. Thus, the stability of enzymeas obtained commercially would differ from enzymes which are bound tobuilder salts by various techniques. There would be differencesdepending upon the particular technique also. However, regardless of theform of the enzyme, stability is. substantially improved whenpercompound in accordance with the invention is employed.

The organic surface active component of the aforementioned washingproducts may be an anionic, nonionic or amphoteric surface activecompound or a mixture of two or more of the foregoing agents may beused.

The anionic surface active agents include those surface active ordetergent compounds which contain an organic hydrophobic group and ananionic solubilizing group in their molecular structure. Typicalexamples of anionic solubilizing groups are sulfonate, sulfate,carboxylate, phosphonate and phosphate.

Examples of suitable anionic detergents which fall within the scope ofthe anionic detergent class include the water-soluble salts, e.g., thesodium, ammonium, and alkylolammonium salts, of higher fatty acids orresin acids containing about 8 to 24 carbon atoms, perferably 10 to 20carbon atoms. Suitable fatty acids can be obtained from oils and waxesof animal or vegetable origin, e.g., tallow, grease, coconut oil, talloil and mixtures thereof. Particularly useful are the sodium andpotassium salts of the fatty acid mixtures derived from coconut oil andtallow, e.g., sodium coconut soap and potassium tallow soap.

The anionic class of detergent also includes the watersoluble sulfatedand sulfonated synthetic detergents having an alkyl radical of 8 to 26,and preferably about 12 to 22 carbon atoms, in their molecularstructure. (The term alkyl includes the alkyl portion of the higher acylradicals.)

Examples of the sulfonated anionic detergents are the higher alkylmononuclear aromatic sulfonates such as the higher alkyl benzenesulfonates containing from 10 to 16 carbon atoms in the alkyl group in astraight or branched chain, e.g., the sodium, potassium and ammoniumsalts of higher alkyl benzene sulfonates, higher alkyl toluenesulfonates, higher alkyl phenol sulfonates, and higher alkyl naphthalenesulfonates. A preferred sulfonate is linear alkyl benzene sulfonatehaving a high content of 3- (or higher) phenyl isomers and acorrespondingly low content (well below 50%) of 2- (or lower) phenylisomers, i.e., wherein the benzene ring is preferably attached in largepart at the 3 or higher (e.g., 4, 5, 6 or 7) position of the alkyl groupand the content of isomers in which the benzene ring is attached at the2 or 1 position is correspondingly low. Particularly preferred materialsare set forth in US. Pat. 3,320,174.

Other suitable anionic detergents are the olefin ulfonates, includinglong chain alkene sulfonates, long chain hydroxyalkane sulfonates ormixtures of alkenesulfonates and hydroxylalkane-sulfonates. These olefinsulfonate detergents may be prepared in a known manner by the reactionof S0 with long chain olefins containing 8 to 25, preferably 12-21,carbon atoms and having the formula RCHz-CHR where R is a higher alkylgroup of 6 to 23 carbons and R is an alkyl group of 1 to 17 carbons orhydrogen to form a mixture of sultones and alkene-sulfonic acids whichis then treated to convert the sultones to sulfonates. Other examples ofsulfate or sulfonate detergents are paraffin sulfonates containing about10-20, preferably about 15-20, carbon atoms, e.g., the primary paraflinsulfonates made by reacting long chain alpha olefins and bisulfites andparafiin sulfonates having the sulfonate groups distributed along theparaffin chain as shown in U.S. Pats. 2,503,280, 2,507,088; 35,260,741;3,372,188 and German Pat. 735,096; sodium and potassium sulfates ofhigher alcohols containing 8 to 18 carbon atoms such as sodium laurylsulfate and sodium tallow alcohol sulfate; sodium and potassium saltsof-- sulfofatty acid esters containing about to 20 carbon atoms, e.g.,methyl sulfomyristate and methyl sulfotallowate; ammonium sulfates ofmonoor di-glycerides of higher fatty acids, e.g., stearic monoglyceridemonosulfate; sodium and alkylolammonium salts of alkyl polyethenoxyether sulfates produced by condensing 1 to 5 moles of ethylene oxidewith one mole of higher (Cg-C13) alcohol; sodium higher alkyl glycerylether sulfonates; and sodium or potassium alkyl phenol poly ethenoxyether sulfates with about 1 to 6 oxyethylene groups per molecule and inwhich the alkyl radicals contain about 8 to about 12 carbon atoms.

The suitable anionic detergents include also the acyl sarcosinates(e.g., sodium lauroylsarcosinate), sodium and potassium salts of thereaction product of higher fatty acids containing 8 to 18 carbon atomsin the molecule esterified with isethionic acid, and sodium andpotassium salts of the higher fatty acid amide of methyl taurine, e.g.,sodium cocoyl methyl taurate and sodium stearoyl methyl taurate.

Anionic phosphate surfactants in which the anionic solubilizing groupattached to the hydrophobic group is an oxyacid of phosphorous are alsouseful in the detergent compositions. Suitable phosphate surfactants arethe sodium, potassium and ammonium alkyl phosphate esters such as (R-O)PO;,M and ROPO M in which R represents an alkyl chain containing fromabout 8 to about 20 carbon atoms or an alkyl phenyl group having 8 to 20carbon atoms and M represents a soluble cation. The compounds formed byincluding about one to 40 moles of ethylene oxide in the foregoingesters, e.g., [RO(Et0) -PO M, are also satisfactory.

The particular anionic detergent salt will be suitably selecteddepending upon the particular formulation and the proportions therein.Preferred salts include the ammonium, substituted ammonium (mono, diandtriethanolarnmonium), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts of the higheralkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates,and

the higher fatty acid monoglyceride sulfates.

The nonionic synthetic organic detergents are generally the condensationproduct of an organic aliphatic or alkyl aromatic hydrophobic compoundand hydrophilic ethylene oxide groups. Practically any hydrophobiccompound having a carboxyl, hydroxy, amido, or amino group with a freehydrogen attached to the nitrogen can be condensed with ethylene oxideto form a nonionic detergent. Further, the length of the polyetheneoxychain can be adjusted to achieve the desired balance between thehydrophobic and hydrophilic elements.

The nonionic detergents include the polyethylene oxide condensate of onemole of alkyl phenol containing from about 6 to about 12 carbon atoms ina straight or branched chain configuration with about 5 to 30 moles ofethylene oxide, e.g., nonyl phenol condensed with 9 moles of ethyleneoxide, dodecyl phenol condensed with 15 moles of ethylene oxide anddinonyl phenol condensed with 15 moles of ethylene oxide. Condensationproducts of the corresponding alkyl thiophenols with 6 to 30 moles ofethylene oxide are also suitable.

Also included in the nonionic detergent class are the condensationproducts of a higher alcohol containing about 8 to 22 carbon atoms in astraight or branched chain configuration condensed with about 5 to 30moles of ethylene oxide, e.g., lauryl-myristyl alcohol condensed withabout 16 moles of ethylene oxide.

Another well known class of nonionic detergents is the condensationproduct of ethylene oxide on a hydrophobic base formed by thecondensation of propylene oxide and propylene glycol. These materialsare sold under the trade name Pluronic. The molecular weight of thehydrophobe ranges from about 1,500 to 1,800 and the polyethylene oxidecontent may comprise up to 50% of the total weight of the condensate.

Other nonionic detergents include the ethylene oxide addends ofmonoesters of hexahydric alcohols and inner ethers thereof with higherfatty acids containing about 10 to 20 carbon atoms, e.g., sorbitanmonolaurate, sorbitan monooleate, and mannitan monopalmitate.

The amphoteric detergents which can be used in the compositions of thisinvention are generally water-soluble salts of derivatives of aliphaticamines which contain at least one alkyl group of about 8 to 20 carbonatoms and an anionic water solubilizing carboxyl, sulfo or sulfate groupin their molecule.

The suitable ampholytic or amphoteric detergents which can be used inthe compositions of thi invention generally contain a hydrophobic alkylgroup of about 8 to 18 carbon atoms, at least one anionicwater-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, orphosphono, and at least one cationic group, e.g., nonquaternarynitrogen, quaternary ammonium, or quaternary phosphonium group, in theirmolecular structure. The alkyl group may be straight chain orbranched'and the specific cationic atom may be part of a heterocyclicring.

Examples of suitable ampholytic detergents include the alkylbetaaminopropionates, RN(H)C H COOM; the alkyl betaiminodipropionates,RN(C H COOM) and the long chain imidazole'derivatives having thefollowing formula:

CH N CH: W R- i J I I4:COOM 1" wherein R is an alkyl group of about 8 to18 carbon atoms, W is selected from the group of R OH, R OM and R ORCOOM, Y is selected from the group consisting of OH, R SO and R OSO R isan alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms, Ris selected from the group consisting of alkyl, alkyl aryl and fattyacyl glyceride groups having 6 to 18 carbon atoms in the alkyl or anacyl group, and M is a water-soluble action, e.g., alkali metal,ammonium or alkylolammonium. Preferred detergents are sodium N- laurylbetaaminopropionate, disodium N-lauryl iminodipropionate, and thedisodium salt of 2-laurylcycloimidium-l-hydroxyl, l-ethoxyethanoic acid,l-ethanoic acid. Other imidazole detergents are described in U.S.2,773,068; U.S. 2,781,354 and U.S. 2,781,357.

Other suitable amphoteric detergents are the sultaine and betaine typeshaving the following general structure:

wherein R is an alkyl group containing about 8 to 18 carbon atoms, R'and R are lower alkyl groups containing 1 to 3 carbon atoms, R, is analkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms,and

X is an anion selected from the group consisting of SO =(sultaine) andCOO=(betaine). Preferred compounds are l-(myristyl dimethylammonio)acetate and 1- (myristyl dimethylammonio) 2-hydroxypropane-3-sulfonate.

Another class of suitable amphoteric detergents is the amphotericimidazoline having the following structure:

wherein R is a higher acyclic group of 7 to 17 carbon atoms. The acyclicgroups may be derived from coconut oil fatty acids (a mixture of fattyacids containing 8 to 18 carbon atoms), lauric fatty acid, and oleicfatty acid and the preferred groups are C -C alkyl groups.

The surface active agent is typically present in amount of about -95% byweight, preferably about -25%.

Various other materials may be present in the washing products. Thus,materials such as the higher fatty acid amides may be added to improvedetergency and modify the foaming properties in a desirable manner.Examples thereof are the higher fatty acid alkanolamides, preferablyhaving 2-3 carbons in each alkanol group attached to a fatty acylradical containing 10-18 carbons (preferably 10-14 carbons), such aslauric or myristic monoethanolamides, diethanolamides andisopropanolamides.

Other suitable foam builders are the tertiary amine oxides of thegeneral formula R R R N 0 wherein R is an alkyl radical of about 10 to18 carbon atoms, R and R are alkyl or hydroxyalkyl groups containing 1to 3 carbon atoms, and the arrow represents a semipolar bond. Includedamong the satisfactory amine oxides are lauryl dimethyl amine oxide andmyristyl dimethyl amine oxide.

In addition to the materials described above, the additional buildersfor the detergent include the water-soluble inorganic builder saltscommonly known in the art, or it may be a water-soluble organicsequestering agent such as sodium nitrilotriacetate, or mixturesthereof. Sodium citrate may be used.

The water-soluble inorganic builder salts may be suitable alkali metal,alkaline earth metal, or heavy metal salt or combinations thereof.Ammonium or an ethanolammonium salt in a suitable amount may be addedalso, but, generally the sodium and potassium salts are preferred.Examples are the water-soluble sodium and potassium phosphates,silicates, carbonates, bicarbonates, borates, sulfates and chlorides.Particularly preferred builder salts are the alkaline builder salts suchas polyphosphates, silicates, borates, carbonates, etc.

In the water-soluble inorganic builder salt mixtures used in thedetergent compositions, it is often preferred to have present a mixtureof sodium tripolyphosphate and sodium or potassium bicarbonate, such asa combination or mixture of salts wherein the bicarbonate totripolyphosphate ratio is selected from the range of about 1:1 to about3: 1.

Both Phase I and Phase II sodium tripolyphosphate and mixtures thereofmay be successfully used in the compositions. The usual commercialtripolyphosphate consists mainly of the Phase H material. The commercialtripolyphosphate material is usually essentially tripolyphosphate, e.g.,87-95%, with small amounts, e.g., 4-13% of other phosphates, e.g.,pyrophosphate and orthophosphate. Sodium tripolyphosphate in itshydrated form may be used also. Trisodium orthophosphate may be used inthe amounts indicated.

The sodium or potassium bicarbonate is an eflective pH buffer. Thebicarbonate may be incorporated directly as anhydrous bicarbonate or inthe form of sesquicarbonate a hydrate containing both bicarbonate andcarbonate.

Generally, when present the builder salt is employed in amount in therange of about 20-90%, preferably at least 25% (e.g., 35 to 80%) of thedetergent composition.

Fatty alcohols of 10-18 carbon atoms such as lauryl or coconut fattyalcohols, or cetyl alcohol are suitable additives also. A hydrotropicmaterial such as the lower alkyl aryl sulfonates, e.g., sodium tolueneor oxylene sulfonates, can assist processing also. In general, thesematerials and the foregoing foam builders are added in minor amounts,usually from about /2 to 10%, preferably 1 to 6%, based on the totalsolids.

If desired, the product of the invention may also include an activatorfor the precompound, such as perborate activator.

The perborate activators are a well known class of materials. Those ofgreatest importance which may be used in the practice of this inventionare compounds which are percarboxylic acid precursors. Such compoundsinclude esters and anhydrides and acyl amides. 'Examples of suitableactivators are the following:

N-acetyl phthalimide N-acetyl succinimide Trisacetyl cyanurate N-benzoylsuccinimide Phenyl acetate Acetylsalicylic acid N-p-anisoyl succinimideN-alpha-napthoyl succinimide N-beta-napthoyl succinimide N-benzoylglutarimide N-p-chlorobenzoyl succinimide N-benzoyl succinimideN-p-chlorobenzoyl-5,5-dimethyl hydantoin N-o-chlorobenzoyl succinimideN-p-chlorobenzoyl phthalimide.

Further examples of suitable activator compounds or the imide type, bothcyclic and aliphatic, have the following structural formula:

0 Rr-(ii-OR wherein R represents alkyl and preferably lower alkyl of lto 4 carbon atoms or aryl such as phenyl and R represents an N-bondedimide radical. Thus, included within the foregoing structural formulaare the following:

N-methoxycarbonyl saccharide N-methoxycarbonyl phthalimideN-ethoxycarbonyl phthalimide N-methoxycarbonyl-S,S-dimethyl hydantoinN-methoxycarbonyl succinimide N-phenoxycarbonyl succinimideN,N-di-(methoxycarbouyl) acetamide N-methoxycarbonyl glutarimide 1,3-di-(N-methoxycarbonyl -hydantoin 1,3-di-(N-methoxycarbonyl)-5,5-dimethylhydantoin.

Other suitable activator compounds are represented according to thefollowing structural formula:

wherein X represents halogen, e.g., chloro, and Z represents the atomsnecessary to complete a heterocyclic nucleus selected from the groupconsisting of hydantoin and succinimide.

Specific representatives of compounds of this type include, withoutnecessary limitation, the following:

N-m-chlorobenzoyl-iidimethyl hydantoin N-m-chlorobenzoylsuccinimide.

Another group of activator compounds comprises N-sulfonated cyclicimides including those of the following structural formula:

wherein R represents lower alkyl of from 1 to 4 carbon atoms and aryland Z represents the atoms necessary to complete a heterocyclic ringselected from the group consisting of succinimide and phthalimide.Specific examples of compounds of this type include, without necessarylimitation, the following:

N-benzenesulfonyl phthalimide N-benzenesulfonyl succinimideN-methanesulfonyl phthalimide N-methanesulfonyl succinimide A furtherclass of activator compounds comprises alkyl and aryl chloroformatederivatives, including for example:

Methylchloroformate Ethylchloroformate Phenylchloroformate Sinceindividual activators vary in structure and molecular Weight as well asperformance, it is convenient to relate the quantity of activator to beemployed to the desired available oxygen present in the particularpercompound being used. For reactive aromatic monoacyl compounds such asmetachlorobenzoyldimethylhydantoin and metachlorobenzoylsuccinimide,strong bleaching is obtained when approximately equimolecular quantitiesof activator and peroxygen are present. Bleaching is enhanced withincrease in the concentration of activator and maintenance of about a1:1 mol ratio of activator and the peroxygen present in the percompound.By increase of the mol ratio of available oxygen to activator, milderbleaching is obtained particularly when the ratio is greater than 2:1.For reactive aliphatic polyacylated compounds such as tetra-acetylethylenediamine, tetra-acetyl hydrazine, triacetyl cyanurate, the moleratio of available oxygen to activator is preferably 2:1, althoughhigher (e.g., 6: 1) or lower (e.g., less than 1: 1) mol ratios may beemployed.

The mixtures may also contain optical brightening agents or fluorescentdyes (e.g., amounts in the range of about V to 35%); germicidalingredients such as halogenated carbanilides, e.g.,trichlorocarbanilide, halogenated salicylanilide, e.g.,tribromosalicylanilide, halogenated bisphenols, e.g., hexachlorophene,halogenated trifluoromethyldiphenyl urea, zinc salt of 1-hydroxy-2-pyridinethione and the like (e.g., in amounts in the range of about to2%); soil-suspending agents such as sodium carboxymethyl cellulose orpolyvinyl alcohol, preferably both, or other soluble polymericmaterials, such as methyl cellulose (the amount of suspending agentbeing in the range of about to 2%); antioxidants such as2,6-di-tert-butylphenol or other phenolic antioxidant materials (e.g.,in amounts in the range of about 0.001 to 0.1%); coloring agents;bleaching agents; and other additives.

A particularly suitable composition, for use as a granular detergentmaterial contains builder salt such as sodium tripolyphosphate and amixture of a linear alkylbenzenesulfonate, as previously described, soapand a nonionic detergent, with the soap and nonionic detergent beingpresent in minor proportions. About 50 to 1000 parts by weight ofbuilder salt are employed per 100 parts by weight of the mixture oflinear alkylbenzenesulfonate, soap and nonionic detergent. The ratios ofthe amounts of (A) soap, and (B) nonionic detergent, to (C) the totalamount of the synthetic anionic sulfonate detergent in the mixture arepreferably as follows: AzC, about 1:10 to 1:2; preferably about 1:4 to1:6, on an anhydrous basis; BzC, about 1:10 to 1:3, e.g., about 1:4 to1:6, on an anhydrous basis. The component (C) is preferably solely alinear alkylbenzenesulfonate although it may comprise a blend of thelinear alkylbenzenesulfonate detergent with other anionic syntheticsulfate or sulfonate detergents (e.g., olefin sulfonates, parafiinsulfonates having the sulfonate groups distributed along the parafiinchain, or alkyl sulfates) with the alkylbenzenesulfonate constituting,say /3, /2 or 36 of this blend.

The following examples are given to illustrate this invention further.In these examples, all proportions are by weight unless otherwisespecified.

EXAMPLE 1 The following detergents are prepared:

The enzymatic granules are prepared from a blend of 3.455 parts ofsodium tripolyphosphate and 0.345 part of the subtilisin enzyme Alcalase(1.5 AU/ g.) which is mixed in an air mixer unit and brought intocontact with a spray 0.130 part of the condensation product of 1 mole ofnonyl phenol and 9 moles of ethylene oxide in solution in 1.020 parts ofwater in a Grun spray-mixer. The thus formed granules are aged to permithydration of the sodium tripolyphosphates.

The proteolytic enzyme preparation used has a maximum proteolyticactivity at a pH of 8-9. This activity as measured at pH 7.5 on thecommercial enzyme preparation available from Novo Industri A/ S,Copenhagen, Denmark, is about 1.5 Anson units per gram of the enzyme.The commercial enzyme preparation is a raw extract of Bacillus subtilisculture and contains about 6% of pure crystallized proteolytic material.The preparation is extremely fine and contains about 6% of purecrystallized proteolytic material. The preparation is an extremely finepowder; typically the particle diameter is mainly below 0.15 mm.,generally above 0.01 mm., e.g., about 0.1 mm., and as much as 50% oreven 75% of the material may be below 0.15 mm. The preparation containsabout 70% of sodium chloride and about 15-18% of sodium sulfate and hasan organic content of about 11%.

The sodium perborate fractions used in each of the two detergents,above, are prepared in Koson unit continuous screen device and are dryblended in an amalgamator.

Each of the detergents are packaged and aged at 43 C. for four weeks andat room temperature.

No enzymatic loss is detected with either of the deterwhile the loss inenzyme activity with Detergent A containing the coarser perborate isonly 17.1%.

EXAMPLE 2 Two additional detergents are prepared identical to those ofExample 1 except that sodium perborate tetrahydrate of the particle sizedistributions indicated below are dry blended in an amalgamator andemployed:

Detergent Diameter of perborate particles D% Greater than 1.68 mm NilNil 0.84-1.68 mm 0. 1 Nil 0.42-0.84 mm- 60. 6 52. 3 0.25-0.42 mm 28.328.4 0.177-0.25 mm- 9. 2 9. 3 0149-0177 mm 1.2 1.7 0074-0149 mm 0. 6 6.l 0.044-0074 mm Nil 2. 0 Less than 0.044 m Nil 1. 1

Detergent D in which the amount of fine particles having a diameter ofless than 0.177 mm. exceeds suffers an enzyme activity loss of 29.6%after packaging and storing for four weeks at room temperature and of46.89% at 43 C., while Detergent C, having less content of fines has itsenzyme activity decreased by only 6.0% after packaging and storing forfour weeks at room temperature and 20.0% at 43 C. 7

EXAMPLE 3 The following detergents are prepared:

Parts Component E F G Sodium dodecylbenzene sulfonate 0.92 0. 92 0. 94Sodium tallow soap 1. 54 1. 54 1. 51 Sodium silicate (NazO/ZSiOr) 1. 541.54 1. 56 Sodium tripolyphosphate 12.80 12. 80 12.59 Sodiumcarboxymethyl cellulose 0. l5 0. 15 0.15 Ethoxylated ell-C15 alcohol(11:1 E0)- 0.66 0.66 0. 64 Moistur 2. 04 2. 04 2. 05 Enzyme granules(1.6 AU/g., 2% moisture) 0.25-0.42 m 0. 18 0. 18 0. 18 Ethoxylated Cr-C15 fatty alcohol (50:1 150)..-. 0.96 0.96 0.96

Sodium perborate tetrahydrate. as indicated below.

Detergent Diameter of perborate particles E% F% (3% Greater than 1.68 mmNil 0.84-1.68 mm.. 0.1 0.42-0.84 mm- 13. 9 0.25-0.42 mm- 66. 50.177-0.25 mm 19. 5 0.1490.177 mm- Nil 0074-0149 mm. Nil 0.044-0074 mm-Nil Less than 0.044 mm Nil After packaging and aging for four weeks atroom temperature none of Detergents E, F and G reveal loss of enzymeactivity. After packaging and aging for four weeks under acceleratedaging conditions at 43 C., Detergent F, which has a large proportion offine particles suifers an enzyme activity loss of 50.6%; Detergent Ewhich contains a large proportion of coarse particles but also containsmore than 5% of very fine particles reveals an enzyme activity loss of42.1%; Detergent G which contains a large proportion of coarse particlesand substantially no files has a loss in enzyme activity of only 30.9%.

In the above examples when enzyme is employed in ungranulated form or isgranulated by means other than those described, improvement in retentionof enzyme activity is also obtained when coarse particles of percompoundin accordance with this invention are employed.

Further, in the above examples sodium perborate tetrahydrate whenreplaced by sodium perborate monohydrate as well as water-soluble alkalimetal percarbonates, perphosphates and persulfates also improveretention of enzyme activity when the percompound has a particle size inaccordance with this invention.

Further, activators for the percompounds may also be employed in theformulations of the above examples.

It will be apparent to those skilled in the art that variations andmodifications of this invention can be made and that equivalents can besubstituted therefor.

I claim:

1. A biological cleaning composition consisting essentially of about5-95% by weight of a water-soluble synthetic, organic surface-activeagent selected from the group consisting of anionic, nonionic,ampholytic and amphoteric surface-active agents and mixtures thereof,about 0.1-10% by weight of a proteolytic enzyme effective in a pH rangeof about 412 and at temperatures above about 10 C. and about 5-30% byweight of a water-soluble inorganic percompound selected from the groupconsisting of alkali and alkaline earth metal perborates, percarbonates,perphosphates and persulfates, said percompound having a size such thatat least about 50% of the particles thereof are retained on a screenhaving sieve openings of 0.42 mm. and less than about 5% of theparticles pass through a screen having sieve openings of 0.177 mm.

2. The biological cleaning composition claimed in claim 1 wherein saidenzyme is a proteolytic subtilisin enzyme.

3. The biological cleaning composition claimed in claim 1 wherein saidpercompound is sodium perborate.

4. The biological cleaning composition claimed in claim 1 wherein saidpercompound is substantially free of particles which pass through ascreen having sieve openings of 0.177 mm.

5. The biological cleaning composition claimed in claim 1 wherein anactivator of the percompound having the structural formula 0 Rt--ORwherein R is selected from the group consisting of lower alkyl andphenyl and R is an N-bonded imide radical is present in the compositionin a mole ratio of available oxygen from the percompound to activator ofabout 1:1 to about 6:1.

6. The biological cleaning composition claimed in claim 1 wherein saidenzyme is in a granule and is bound to sodium tripolyphosphate detergentbuilder salt.

7. The biological cleaning composition claimed in claim 3 wherein saidsodium perborate is sodium perborate tetrahydrate.

References Cited UNITED STATES PATENTS 3,519,379 7/l970 Blomeyer et al.252-99 X 3,637,339 1/ 1972 Gray 252-99 X 3,664,961 5/1972 Norris--252-99 MAYER WEINBLA'IT, Primary Examiner U.S. c1. X.R. 252Dig. 12

